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Related Concept Videos

Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Bubble nucleation in polymer–CO2 mixtures.

Xiaofei Xu1, Diego E Cristancho, Stéphane Costeux

  • 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.

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Bubble nucleation in polymer–CO2 mixtures is studied. A critical temperature reveals a phase transition affecting nucleation barriers, with classical theory failing to predict results.

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Area of Science:

  • Materials Science
  • Chemical Engineering
  • Computational Chemistry

Background:

  • Bubble nucleation is crucial for polymer processing with supercritical fluids.
  • Understanding nucleation in polymer–CO2 mixtures informs material design and process optimization.

Purpose of the Study:

  • To investigate bubble nucleation in poly(methyl methacrylate)–CO2 and polystyrene–CO2 systems.
  • To determine the influence of initial CO2 pressure and temperature on nucleation barriers.
  • To compare computational findings with classical nucleation theory.

Main Methods:

  • Density-functional theory (DFT) combined with the string method.
  • Simulating bubble nucleation under varying pressure and temperature conditions.
  • Analyzing the free energy pathway of bubble formation.

Main Results:

  • A discontinuous drop in nucleation barrier observed below a critical temperature, linked to a CO2-rich phase transition.
  • Nucleation barrier is higher for polystyrene–CO2 than for poly(methyl methacrylate)–CO2.
  • Classical nucleation theory inaccurately predicts bubble nucleus structure and underestimates the nucleation barrier.

Conclusions:

  • The study reveals complex nucleation behavior in polymer–CO2 systems, driven by phase transitions.
  • Polystyrene–CO2 requires higher temperatures and pressures to achieve experimentally relevant nucleation barriers compared to poly(methyl methacrylate)–CO2.
  • DFT and string method provide a more accurate description of bubble nucleation than classical theories.